US3157685A - Partial esters of phosphoric acid and a method of preparing them - Google Patents

Partial esters of phosphoric acid and a method of preparing them Download PDF

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US3157685A
US3157685A US177739A US17773962A US3157685A US 3157685 A US3157685 A US 3157685A US 177739 A US177739 A US 177739A US 17773962 A US17773962 A US 17773962A US 3157685 A US3157685 A US 3157685A
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phosphoric acid
preparing
triester
acid
reaction
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Szabo Karoly
Jr Joseph R Froli
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Stauffer Chemical Co
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Stauffer Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl compounds

Definitions

  • This invention relates to organophosphorus compounds and, in particular, to partial esters of phosphoric acid wherein one of the esterifying groups is an unsaturated radical. More specifically, the invention is concerned with allyl hydrogen arylphosphates and to a new and novel method of preparing them.
  • the present invention contem plates a new class of partial diesters of phosphoric acid in which one of the esterifying groups is a lower unsaturated aliphatic radical and the other is an aryl radical and the provision of such partial esters and a novel method of preparing them constitute the primary objects and purposes of the invention.
  • the above described phosphoric diesters were discovered as a product of a new and unexpected chemical reaction involving the cleavage of a neutral triester of phosphoric acid at mildly elevated temperatures and in the presence of an amine salt. Included in the triester group ings is one aryl group and two unsaturated aliphatic groups of the allyl type. During the course of the reaction, an unsaturated aliphatic hydrocarbon residue is eliminated and the resulting diester obtained in the form of its amine salt. At the same time the acid radical of the amine salt becomes associated with the hydrocarbon fragment. Thus, in the event the amine salt is a hydrohalide, there is produced an aliphatic halide. For illustrative purposes, the reaction is depicted in the chemical equation outlined below in which the neutral triester is diallyl phenyl phosphate and the amine salt is triethylamine hydrochloride:
  • R is hydrogen or a lower alkyl radical, e.g. methyl, ethyl, n-propyl, isobutyl, etc.
  • Ar designates an aromatic hydrocarbon residue of the benzene and naphthalene series wherein the hydrocarbon residue can be substituted by such organic groups as lower alkyl, lower alkoxyl, chlorine, bromine, nitro and the like.
  • Exemplary compounds encompassed bythe above depicted general formula include the following specific configurations:
  • Neutral triester phosphates suitable for practicing the invention are defined by the following general formula:
  • Amine salts are likewise known entities and can be found in the prior art. Generally excellent results are achieved by using a trialkylamine hydrochloride and, in this connection, mention is made of the lower members of this series, e.g. trimethylamine hydrochloride, triethylamine hydrochloride, etc;
  • Other suitable amine salts are exemplified by the hydrochlorides of cyclic nitrogenous bases in which the nitrogen atoms thereof are in the tertiary state as typified by pyridine, quinoline, isoquinoline, and the like.
  • the acidic diester phosphates of the invention are readily prepared by heating the amine hydrochloride and neutral triester phosphate in a normally liquid relatively inert organic solvent.
  • Suitable reaction media are provided by the aromatic and saturated hydrocarbons such as benzene, toluene, xylene, hexane, heptane, kerosene as well as the chlorinated derivatives thereof.
  • the triester phosphates are obtained by reacting a phosphorochloridate with a phenol in the presence of a tertiary amine at a temperature below about 50 C. Under these conditions, there is also formed the hydrohalide of the amine.
  • the reaction products are thus a neutral triester phosphate and an amine salt which constitute the requisite starting materials for practicing the process of the invention.
  • the temperature of the reaction mixture is then increased whereby cleavage of the triester is effected with concomitant formation of the desired acid diester phosphate. In general, a temperature above about C. has been found to result in smooth cleavage of the triester.
  • the new compounds of the invention have been found to possess phytocidal activity and are therefore useful in the formulation of herbicidal compositions for the control of vegetation. They are, moreover, valuable as chemical intermediates in further syntheses through their functional group.
  • the free OH group can be esterified with a variety of alcohols thereby giving rise to new and useful mixed triester phosphates.
  • the diesters dissolve in alkaline medium and form water soluble salts by replacement of the hydrogen with an ammonium radical, basic metals, e.g. sodium, potassium, barium, calcium, etc. It is to be understood that the salts of the acid diesters are included within the scope of the invention.
  • the reaction mixture was poured into water and the organic layer separated, washed with a 5% sodium hydroxide solution and the alkali extract combined with the aqueous filtrate obtained in the first separation.
  • the combined aqueous portions were acidified with concentrated hydrochloric acid and the resultant oily precipitate extracted with chloroform.
  • the extract was dried over anhydrous magnesium sulfate, the dessicant filtered off, and the organic solvent removed by distillation in vacuo, the final temperature being 90 C. at 8 mm. There was obtained a brownish oil having a refractive index of 1.5463. Fractionation of the toluene layer yielded 40 g. of allyl chloride by-product.
  • the above prepared allyl 2-chloro-4-nitrophenyl phosphoric acid can be converted into its sodium salt by reaction with sodium rnethoxide in alcoholic solution.
  • the sodium salt is a yellow powder, melting above 250' C.
  • Example 1 The following examples were prepared by procedures patterned after that given for Example 1.
  • frlorrtlJ diallyl p-nitrophenylphos- N n 1.5384. p a e.
  • R is selected from the class consisting of hydrogen and lower alkyl and Ar represents an aromatic hydrocarbon residue selected from the class consisting of naphthyl, phenyl and substituted phenyl wherein the substituents are selected from the class consisting of chlorine, lower alkyl, nitro, lower alkoxyl and bromine, which comprises cleaving, in the presence of an amine salt selected from the class consisting of the hydrochlorides of lower trialkylamine and pyridine, a neutral triester phosphate of the following formula wherein R and Ar have the significance as above set forth and isolating the so-formed diester phosphate from the reaction mixture.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Description

United States Patent ()fiice 3,157,685 Patented Nov. 17, 1964 This invention relates to organophosphorus compounds and, in particular, to partial esters of phosphoric acid wherein one of the esterifying groups is an unsaturated radical. More specifically, the invention is concerned with allyl hydrogen arylphosphates and to a new and novel method of preparing them.
In its broadest aspects, the present invention contem plates a new class of partial diesters of phosphoric acid in which one of the esterifying groups is a lower unsaturated aliphatic radical and the other is an aryl radical and the provision of such partial esters and a novel method of preparing them constitute the primary objects and purposes of the invention.
Other objects will become manifest as the description proceeds.
The above described phosphoric diesters were discovered as a product of a new and unexpected chemical reaction involving the cleavage of a neutral triester of phosphoric acid at mildly elevated temperatures and in the presence of an amine salt. Included in the triester group ings is one aryl group and two unsaturated aliphatic groups of the allyl type. During the course of the reaction, an unsaturated aliphatic hydrocarbon residue is eliminated and the resulting diester obtained in the form of its amine salt. At the same time the acid radical of the amine salt becomes associated with the hydrocarbon fragment. Thus, in the event the amine salt is a hydrohalide, there is produced an aliphatic halide. For illustrative purposes, the reaction is depicted in the chemical equation outlined below in which the neutral triester is diallyl phenyl phosphate and the amine salt is triethylamine hydrochloride:
Toluene EtrN-HCI 110 C.
wherein R is hydrogen or a lower alkyl radical, e.g. methyl, ethyl, n-propyl, isobutyl, etc. and Ar designates an aromatic hydrocarbon residue of the benzene and naphthalene series wherein the hydrocarbon residue can be substituted by such organic groups as lower alkyl, lower alkoxyl, chlorine, bromine, nitro and the like. Exemplary compounds encompassed bythe above depicted general formula include the following specific configurations:
Compound 10 Compound 11 Compound 12 N0 l 0H,:CH-CH -li-OQ-NO;
H CgH5 H3 Compound 13 Compound 19 The neutral triester phosphates which serve as the precursors of the diesters of the invention, are in some instances known compounds and are described in the chemical literature. They are commonly obtained by the reaction of a phosphorochloridate with a salt of a phenol. The reaction is carried out at a relatively low temperature, i.e., in the neighborhood of 50 C.
Neutral triester phosphates suitable for practicing the invention are defined by the following general formula:
II CHR=CHCH O (I) wherein R and Ar have the significance as previously enumerated.
Amine salts, the presence of which facilitates the formation of the acidic diesters, are likewise known entities and can be found in the prior art. Generally excellent results are achieved by using a trialkylamine hydrochloride and, in this connection, mention is made of the lower members of this series, e.g. trimethylamine hydrochloride, triethylamine hydrochloride, etc; Other suitable amine salts are exemplified by the hydrochlorides of cyclic nitrogenous bases in which the nitrogen atoms thereof are in the tertiary state as typified by pyridine, quinoline, isoquinoline, and the like. The acidic diester phosphates of the invention are readily prepared by heating the amine hydrochloride and neutral triester phosphate in a normally liquid relatively inert organic solvent. Suitable reaction media are provided by the aromatic and saturated hydrocarbons such as benzene, toluene, xylene, hexane, heptane, kerosene as well as the chlorinated derivatives thereof.
If desired, it is not necessary to isolate the intermediate neutral triester phosphate from which are derived the acid diesters of the invention. As above pointed out, the triester phosphates are obtained by reacting a phosphorochloridate with a phenol in the presence of a tertiary amine at a temperature below about 50 C. Under these conditions, there is also formed the hydrohalide of the amine. The reaction products are thus a neutral triester phosphate and an amine salt which constitute the requisite starting materials for practicing the process of the invention. The temperature of the reaction mixture is then increased whereby cleavage of the triester is effected with concomitant formation of the desired acid diester phosphate. In general, a temperature above about C. has been found to result in smooth cleavage of the triester.
The new compounds of the invention have been found to possess phytocidal activity and are therefore useful in the formulation of herbicidal compositions for the control of vegetation. They are, moreover, valuable as chemical intermediates in further syntheses through their functional group. Thus, the free OH group can be esterified with a variety of alcohols thereby giving rise to new and useful mixed triester phosphates. Because of the acidic nature of the OH group, the diesters dissolve in alkaline medium and form water soluble salts by replacement of the hydrogen with an ammonium radical, basic metals, e.g. sodium, potassium, barium, calcium, etc. It is to be understood that the salts of the acid diesters are included within the scope of the invention.
Reference is now made to the following examples which are presented for the purpose of illustration only since variations in practicing the invention without departing from the spirit or scope thereof will be apparent to those skilled in the art to which the said invention pertains.
EXAMPLE 1 All l 2-Chloro-4-Nitrophenylphosphoric Acid 195.5 g. of diallyl phosphorochloridate was added dropwise to a mixture of 173.5 g. of 2-chloro-4-nitrophenol, 101 g. of triethylamine and 400 ml. of toluene. The mixture was thoroughly stirred during the addition and the reaction which was exothermic was maintained at 45-50 C. by external cooling. The triethylamine hydrochloride precipitated out during the course of the reaction. Following addition of the diallyl phosphorochloridate, the mixture was refluxed C.) for 4 hours after which time the temperature had fallen to 92 C., and all of the triethylamine hydrochloride had dissolved. The reaction mixture was poured into water and the organic layer separated, washed with a 5% sodium hydroxide solution and the alkali extract combined with the aqueous filtrate obtained in the first separation. The combined aqueous portions were acidified with concentrated hydrochloric acid and the resultant oily precipitate extracted with chloroform. The extract was dried over anhydrous magnesium sulfate, the dessicant filtered off, and the organic solvent removed by distillation in vacuo, the final temperature being 90 C. at 8 mm. There was obtained a brownish oil having a refractive index of 1.5463. Fractionation of the toluene layer yielded 40 g. of allyl chloride by-product.
The above prepared allyl 2-chloro-4-nitrophenyl phosphoric acid can be converted into its sodium salt by reaction with sodium rnethoxide in alcoholic solution. The sodium salt is a yellow powder, melting above 250' C.
EXAMPLE 2 Allyl Pentaclzlorophenylphosphoric Acid This compound was prepared following the procedure given for Example 1 but substituting pentachlorophenol for 2-chloro-4-nitrophenol of the previous example. The resulting diallyl 2-chloro-4-nitrophenylphosphate, on cleavage, yielded a white solid, which, after crystallization from acetone, melted at 164 C. The product corresponded to the above named compound.
The following examples were prepared by procedures patterned after that given for Example 1.
Example Description 3 Allyl 4,G-dinitro-o-cresylphosphoric Brown oil,
acid; from diallyl 4,6-dinitro-phenyl- N1325=1.5435. phosphate.
4 Allyl 2-sec. butyl 4,6-dinitrop11enyl- Brown oil,
phosphoric acid; from diallyl 2-sec. ND =1.53O0. butyl-4,e-dinitrophenylphosphate.
5 Allyl p-nitrophenylphosphoric acid; Brown oil,
frlorrtlJ diallyl p-nitrophenylphos- N n 1.5384. p a e.
6 Allyl 2,4,5-trichlorophenylphosphoric Light brown oil,
acid; from diallyl trichlorophenyl- ND =1.5358. phosphate.
7 Allyl phcnylphosphoric acid; from Light brown oil,
diallyl phenylphosphate. Nn =1.5095.
We claim:
1. A method of preparing a diester phosphate as represented by the following general formula:
wherein R is selected from the class consisting of hydrogen and lower alkyl and Ar represents an aromatic hydrocarbon residue selected from the class consisting of naphthyl, phenyl and substituted phenyl wherein the substituents are selected from the class consisting of chlorine, lower alkyl, nitro, lower alkoxyl and bromine, which comprises cleaving, in the presence of an amine salt selected from the class consisting of the hydrochlorides of lower trialkylamine and pyridine, a neutral triester phosphate of the following formula wherein R and Ar have the significance as above set forth and isolating the so-formed diester phosphate from the reaction mixture.
2. The method according to claim 1 wherein the amine salt is triethylamine hydrochloride.
3. The method according to claim 1 wherein the reaction is carried out in the presence of a normally liquid aromatic solvent.
References Cited in the file of this patent UNITED STATES PATENTS Graves June 18, Farrington et al. Nov. 22, Smith et al. May 23, Weisel et al. Feb. 20, Gamrath Oct. 20, Morris Apr. 6, Bell et al. Apr. 22, Saul June 30, Snyder Jan. 26, Norman Sept. 13, Arakelian et al. Oct. 17, Whetstone Mar. 27.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,157,685 7 November 17, 1964 Karoly Szabo et al.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 2, lines 38 to 42, Compound 8 should appear as shown below instead of as in the patent:
G O l CH =CHCH O--I:O Cl lines 45 to 48, Compound 9 should appear as shown below instead of as in the patent:
same column 2, lines 55 to 60, Compound 11 should appear as shown below instead of as in the patent:
Signed and sealed this 30th day of March 1965.
(SEAL) Attest:
, ERNEST W, SWIDER EDWARD J. BRENNER ,t, esting Officer Commissioner of Patents

Claims (1)

1. A METHOD OF PREPARING A DIESTER PHOSPHATE AS REPRESENTED BY THE FOLLOWING GENERAL FORMULA:
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3284540A (en) * 1965-03-15 1966-11-08 Dal Mon Research Co Alkyd copolymers of halogen-containing phosphonium monomers and polymers
US3346386A (en) * 1962-12-17 1967-10-10 Agfa Ag Polycondensation products of phosphoric acid amides with aliphatic polyethers as developer adjuvants
US3928018A (en) * 1972-02-29 1975-12-23 Gaf Corp N-substituted-p-(2-chloroethyl)-phosphonamidates as yield improvers

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2005619A (en) * 1934-11-10 1935-06-18 Du Pont Esters of acids of phosphorus
US2488662A (en) * 1946-06-25 1949-11-22 California Research Corp Metal organo-phosphates
US2508432A (en) * 1949-09-06 1950-05-23 California Research Corp Bitumen-treating agent
US2542604A (en) * 1948-12-01 1951-02-20 Standard Oil Dev Co Extreme pressure lubricant and extreme pressure agents therefor
US2656374A (en) * 1950-05-01 1953-10-20 Monsanto Chemicals Process for the preparation of alkyl phenyl phosphoric acids and the salts thereof
US2674616A (en) * 1951-08-18 1954-04-06 Shell Dev Preparation of phosphoruscontaining amine salts
US2831881A (en) * 1955-09-23 1958-04-22 Shell Dev Amine salts of trihalomethanephos-phonic and trihalomethanephos-phinic acids
US2892751A (en) * 1956-04-25 1959-06-30 Monsanto Chemicals Haloalkenyl phosphorothioates
US2922739A (en) * 1958-01-31 1960-01-26 Du Pont O-hydrocarbon, s-(quaternary ammonium-substituted alkyl) esters of phosphorothioic acids and insecticidal compositions thereof
US2952699A (en) * 1955-12-23 1960-09-13 Lubrizol Corp Preparation of substituted phosphoric acids
US3004996A (en) * 1956-04-09 1961-10-17 Lubrizol Corp Phosphorus and sulfur containing compositions and method for preparing same
US3027296A (en) * 1956-05-28 1962-03-27 Shell Oil Co Halogenated phosphorus esters

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2005619A (en) * 1934-11-10 1935-06-18 Du Pont Esters of acids of phosphorus
US2488662A (en) * 1946-06-25 1949-11-22 California Research Corp Metal organo-phosphates
US2542604A (en) * 1948-12-01 1951-02-20 Standard Oil Dev Co Extreme pressure lubricant and extreme pressure agents therefor
US2508432A (en) * 1949-09-06 1950-05-23 California Research Corp Bitumen-treating agent
US2656374A (en) * 1950-05-01 1953-10-20 Monsanto Chemicals Process for the preparation of alkyl phenyl phosphoric acids and the salts thereof
US2674616A (en) * 1951-08-18 1954-04-06 Shell Dev Preparation of phosphoruscontaining amine salts
US2831881A (en) * 1955-09-23 1958-04-22 Shell Dev Amine salts of trihalomethanephos-phonic and trihalomethanephos-phinic acids
US2952699A (en) * 1955-12-23 1960-09-13 Lubrizol Corp Preparation of substituted phosphoric acids
US3004996A (en) * 1956-04-09 1961-10-17 Lubrizol Corp Phosphorus and sulfur containing compositions and method for preparing same
US2892751A (en) * 1956-04-25 1959-06-30 Monsanto Chemicals Haloalkenyl phosphorothioates
US3027296A (en) * 1956-05-28 1962-03-27 Shell Oil Co Halogenated phosphorus esters
US2922739A (en) * 1958-01-31 1960-01-26 Du Pont O-hydrocarbon, s-(quaternary ammonium-substituted alkyl) esters of phosphorothioic acids and insecticidal compositions thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3346386A (en) * 1962-12-17 1967-10-10 Agfa Ag Polycondensation products of phosphoric acid amides with aliphatic polyethers as developer adjuvants
US3284540A (en) * 1965-03-15 1966-11-08 Dal Mon Research Co Alkyd copolymers of halogen-containing phosphonium monomers and polymers
US3928018A (en) * 1972-02-29 1975-12-23 Gaf Corp N-substituted-p-(2-chloroethyl)-phosphonamidates as yield improvers

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